JPS59187640A - Polyamide tire cord and production thereof - Google Patents
Polyamide tire cord and production thereofInfo
- Publication number
- JPS59187640A JPS59187640A JP6119483A JP6119483A JPS59187640A JP S59187640 A JPS59187640 A JP S59187640A JP 6119483 A JP6119483 A JP 6119483A JP 6119483 A JP6119483 A JP 6119483A JP S59187640 A JPS59187640 A JP S59187640A
- Authority
- JP
- Japan
- Prior art keywords
- cord
- polyamide
- mde
- yarn
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Lining Or Joining Of Plastics Or The Like (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明はハイモジュラスで寸法安定性の改善されたポリ
アミドタイヤコード(以下ポリアミドコードと称す)の
簡略化された製造方法に関するものである。従来から自
動車のバイアスタイヤに於てはポリアミドコードが強靭
性、耐久性等の利点を活かして有用されてきた。しかし
乍ら近年、タイヤ構造がバイアスタイヤからラジアルタ
イヤへの移行が進むと共にポリアミドコード(・よその
ンエアを失いつつある。ラジアルタイヤ用コードは特に
ハイモジュラス、寸法安に性が求められ′るがモジュラ
ス、寸法安定性に劣る従来のポリアミドコードは、特に
耐久性を強く求められる分野に限定して一部用いられる
にすぎず、主としてポリエステルコード及びスチールコ
ードが用いられている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a simplified method for producing polyamide tire cord (hereinafter referred to as polyamide cord) having high modulus and improved dimensional stability. Polyamide cords have traditionally been useful in automobile bias tires due to their advantages such as toughness and durability. However, in recent years, with the shift in tire structure from bias tires to radial tires, polyamide cords are losing their air quality.Cords for radial tires are particularly required to have high modulus, low dimensions, and performance. Conventional polyamide cords, which are inferior in modulus and dimensional stability, are only partially used in fields where durability is particularly required, and polyester cords and steel cords are mainly used.
しかしポリエステルコードは小型ラジアルタイヤに有用
されているものの耐熱性、接着性、耐疲労性が劣る為、
苛酷な条件下で使用される大型タイヤへの適用には不安
が持たれている。However, although polyester cord is useful for small radial tires, it has poor heat resistance, adhesion, and fatigue resistance.
There are concerns about its application to large tires that are used under harsh conditions.
一方スチールコードは優れた特性を有するもののタイヤ
重量が増し、燃費を喰うという欠点がある。そこで比較
的大型のラジアルタイヤ用、特にカーンyス材としては
むしろポリアミドコードがその本来の特徴を保持しなが
らポリエステルコードレベルのハイモジュラス性、寸法
安定性を兼備できることが最も好ましく、その開発が望
まれていた。On the other hand, although steel cord has excellent characteristics, it has the drawback of increasing tire weight and reducing fuel consumption. Therefore, it is most preferable to use polyamide cord as a material for relatively large radial tires, especially as a carbon fiber material, because it can maintain its original characteristics while also having the high modulus and dimensional stability of polyester cord, and its development is desirable. It was rare.
しかし品質的に上記すぐれた特性例与を達成することと
同時に従来の方法よりも簡1′t16化されたプロセス
によって貼コストで製造できるようにすることが、ポリ
アミドコードが他素材と競争して確実に利用されるよう
になる為に必要である。これは近年有機繊維の1京料の
価格の上昇が著しく、なかんづくポリアミドは上昇率が
高く、将来(こ渥って原料価格面での不利が予想される
為であり、品質ばかりでなく、製造コスト面ても大巾な
改善が求められているからである。However, in addition to achieving the above-mentioned excellent characteristics in terms of quality, it is also possible to manufacture the cord at a lower cost through a process that is simpler than conventional methods, making polyamide cord competitive with other materials. This is necessary to ensure that it is used. This is because the price of organic fibers has increased significantly in recent years, and the rate of increase is especially high for polyamide, which is expected to be disadvantageous in terms of raw material prices in the future. This is because drastic improvements are required in terms of cost as well.
そこて本発明者らはポリアミドコードが本来の特性を保
持しながら、ハイモジュラス性、寸法安定性を改善し、
且つ該コードを簡略化されたプロセスによって安価に製
造する方法について鋭意検討した結果、本発明に到達し
た。Therefore, the present inventors improved the high modulus and dimensional stability of the polyamide cord while retaining its original properties.
Further, as a result of intensive study on a method of manufacturing the cord at low cost through a simplified process, the present invention was arrived at.
即ち本発明は実質的にポリヘキサメチレンアジパミドか
らなるポリアミドを紡糸速度5oon1n/分以上で溶
融紡糸して得た伸度Eが60%以下、複屈折△nが42
XiO’以上、密度ρが1168以上、単糸繊度Dfが
15〜6デニールのマルテフィラメントを延伸すること
なく、撚係数Kが2200〜28oOで上撚及び下撚を
施し゛(生コードとなし、次いで接着剤を付与したのち
、60〜1oo%のストレッチをがけて緊張熱処理して
下記特性を有するタイヤコードとすることによって達せ
られる。That is, the present invention melt-spun polyamide consisting essentially of polyhexamethylene adipamide at a spinning speed of 5 oon1 n/min or more, and obtained an elongation E of 60% or less and a birefringence Δn of 42
XiO' or more, density ρ is 1168 or more, single filament fineness Df is 15 to 6 deniers, and without drawing, the twisting coefficient K is 2200 to 28oO, and the first and second twists are applied (raw cord and untwisted). This can be achieved by applying an adhesive, applying a 60 to 10% stretch, and subjecting it to tension heat treatment to obtain a tire cord having the following properties.
(イ)T/D、’≧ 6.5g/d
(口l M D E ≦ 8 %(ハ)
へ864%
に) MDE+ハS≦12%
(ホ)l 19QO,4に≧1000但し上記に於て
T/Dは強度、MDEは中間伸度、△Sは177℃乾熱
収縮率、Kは撚係数であり、その定義及び測定法は次の
通りである。(B) T/D,'≧6.5g/d (MDE≦8% (C)
to 864%) MDE+HaS≦12% (E)l 19QO, 4≧1000 However, in the above, T/D is strength, MDE is intermediate elongation, △S is 177℃ dry heat shrinkage rate, K is It is a twist coefficient, and its definition and measurement method are as follows.
複屈折△n°nコニ(株)lQxTp−11型偏光顕微
鏡を用い、白色光を光源とし、通常のペンツクコンペン
セーター法で測定した。Birefringence Δn°n was measured using a polarizing microscope model 1QxTp-11 manufactured by Koni Co., Ltd., using white light as a light source, and by the usual Pentz compensator method.
密度ρ:四塩化炭素を重液、トルエンを軽液として作製
した密度勾配管を用い25℃で測定した。Density ρ: Measured at 25°C using a density gradient tube prepared using carbon tetrachloride as a heavy liquid and toluene as a light liquid.
強度T/D 、伸度E及び中間伸度MDF: : JI
SL1017の定犠及び測定法によった。20℃、65
%Rt(の温湿度に調整された部屋で24時[(4以上
放置後、11テンシロン”IJTM−4L型引張試験機
(東洋ボールドウィン(株)製)を用い、試料長25L
:1n、引張速度30α/分で測定した。Strength T/D, elongation E and intermediate elongation MDF: : JI
According to the sacrificial and measurement method of SL1017. 20℃, 65
%Rt (24 hours) in a room adjusted to a temperature and humidity of
:1n, and the tensile rate was 30α/min.
中間伸度MDE:@EのT/Dと同じ方法でタイヤコー
ドの引張試験を行ない、荷重−伸長率曲線を得る。該荷
重−伸長率曲線に於て、原糸の繊度をD、合撚糸数をn
とした時、荷重時の伸度を求め、これをMDEとする。Intermediate elongation MDE: Perform a tensile test on the tire cord in the same manner as T/D of @E to obtain a load-elongation rate curve. In the load-elongation rate curve, the fineness of the raw yarn is D, and the number of twisted yarns is n.
When , the elongation under load is determined and this is defined as MDE.
MDIDはタイヤコードのモジュラスの目安として矢用
的に用いられるパラメータであり、MDEが小さいほど
モジュラスが高いことを意味する。MDID is a parameter that is used as an indicator of the modulus of a tire cord, and the smaller the MDE, the higher the modulus.
乾熱収縮率△S°試料を 状に倦取り、20℃、65%
RHの温湿度に調節された部屋で24時間以上放置後、
試料の0.1g/dに相当する荷重をかけて測定された
長さくloの試料を無張力状態で177℃のガープ/甲
に30分間放置したのち、オーブンから取り出し、前記
温湿度調節室で4時間放置し、再び上記荷重をかけて測
定した長さllから次式により算出した。Dry heat shrinkage rate △S° sample was cut into shape, 20℃, 65%
After leaving it for more than 24 hours in a room controlled by RH temperature and humidity,
A sample of length lo, measured by applying a load equivalent to 0.1 g/d of the sample, was left in a 177°C Garp/Instep for 30 minutes without tension, then removed from the oven and placed in the temperature/humidity control room. After being left for 4 hours, the above load was applied again and the measured length 11 was calculated using the following formula.
△S=C(lo 〜(1+ )/(Jo X 100
(%)撚係数K 処理コードの10cIN当りの撚数y
2T(但し上撚と下撚数の平均随とする)、繊度をDと
した時、次式で求められる値である。△S=C(lo ~(1+)/(Jo X 100
(%) Twist coefficient K Number of twists per 10 cIN of processed cord y
2T (however, the number of twists is the average of the number of first and second twists), and the fineness is D, the value is determined by the following formula.
但し、繊度は接着剤付着量による補正を行なわない値と
した。However, the fineness was set to a value without correction based on the amount of adhesive attached.
K=T、/’T
従来から紡糸引取光を、延伸工程を省略して撚糸し、接
着剤付与したのちの緊張熱処理時に延伸工程を含めて処
理する簡略化したプロセスについては提案が為されてぎ
た。K=T, /'T Conventionally, proposals have been made for a simplified process in which the fibers are twisted without the stretching process, and the stretching process is included in the tension heat treatment after applying an adhesive. I got it.
例えば特開昭49−133648号公報、および特開昭
54−54415号公報の方法がある。前者は3000
m/分以」二の高速で紡糸したポリアミド又はポリエ
ステル繊維、後者は3000 m7分以上、例えば40
00〜4700m/分の高速で紡糸して得られたナイロ
ン6m維を前記と同様簡略化された方法で処理コードと
する方法である。For example, there are methods disclosed in Japanese Patent Application Laid-open Nos. 49-133648 and 54-54415. The former is 3000
polyamide or polyester fibers spun at a high speed of 2 m/min or more, the latter at 3000 m/min or more, e.g.
This method uses a nylon 6m fiber obtained by spinning at a high speed of 00 to 4,700 m/min to form a treated cord using the same simplified method as described above.
しかし乍ら上記方法は実用的には採用されに<<、その
原因は、上記方法で得られるコードが通常の方法で得ら
れるコードと同等以上の特性とならないことによる。又
撚糸後、接着剤付与後の緊張熱処理時のストレッチによ
って減少する撚数分を予め加味して撚糸しておかねばな
らないが、この場合、ストレッチ前の生コードは繊度が
太い為に撚係数が著しく大きくなり、不均一な撚が発生
する等正常な撚糸ができなくなったり、強力低下も大き
い。又、撚糸数を多くすることはせっかくの簡略化プロ
セスのメリットが活かせないことンこもなる。一方従来
の生コードと同一の撚数をかけた場合は緊張熱処理時の
ストレッチ分だけ撚数が減少する為、特に耐疲労性が低
下してしまう。However, the above method is not practically adopted because the code obtained by the above method does not have characteristics equal to or better than those obtained by a conventional method. In addition, after twisting, it is necessary to take into account the number of twists that will decrease due to stretching during tension heat treatment after applying adhesive, but in this case, the twist coefficient will be lower because the raw cord before stretching has a thicker fineness. The yarn becomes extremely large, causing non-uniform twisting, making it impossible to twist the yarn normally, and causing a significant decrease in strength. In addition, increasing the number of twists may prevent the advantage of the simplified process from being utilized. On the other hand, if the same number of twists as the conventional raw cord is applied, the number of twists will be reduced by the amount of stretching during the tension heat treatment, resulting in particularly poor fatigue resistance.
そこで本発明者らは上記相矛盾−!1″る課題を解決す
る為検討した結果前記方法によって達成できることを見
出した。即ち、本発明は
1)耐疲労性が著しく改善され、且つ、残留伸度が小さ
い繊維を製造することによって2)処理コード撚係数が
従来コードよりも小さくても従来コードと同等以上の耐
疲労性を有するニードが得られるよう?こなったこと、
及び
5)コード緊張熱処理時ストレッチ前が比較的小さくて
済むようtこなったこと
によってはじめて可能となったものである。そして上記
撚係数を減少することtこよって発現するハイモジュラ
ス、寸法安定性等の有用性を活用したコード設計を提案
するものである。Therefore, the present inventors solved the above-mentioned contradiction-! As a result of studies conducted to solve the above problems, it was found that the present invention can achieve the above-mentioned problems by 1) producing fibers with significantly improved fatigue resistance and low residual elongation; 2) Even if the treated cord twist coefficient is smaller than the conventional cord, it is possible to obtain a needle with fatigue resistance equal to or higher than that of the conventional cord.
and 5) This became possible for the first time because the length before stretching during the cord tensioning heat treatment was made relatively small. The present invention also proposes a cord design that takes advantage of the high modulus, dimensional stability, etc. that are produced by reducing the twist coefficient.
次に本発明について図面を用いて説明する。Next, the present invention will be explained using the drawings.
図面は本発明のコードtこ供する原糸の製造工程を示す
。The drawings show the manufacturing process of the yarn used for the cord of the present invention.
本発明eこ用いる繊維は実質的にポリヘキサメ 8−
チレンアジバミドからなるポリアミドからなり、ヘキサ
メチレンアジパミド単位が95モル%以上である共重合
ポリマ又はブレンドポリマを含む。共重合しうるポリマ
成分としてはε−カプラミド、ヘキサメテレンセバヵミ
ド、ヘキサメチレンテレフタラミド、ヘキサメチレンイ
ソフタラミド等があり、ブレンドしうるポリマとしては
上記共重合しうる成分をそれぞれ重合してなるポリマが
ある。本発明の高強力タイヤコードを得る為には25℃
、ポリマ製置1重量%で測定した硫酸相対粘度60以上
である高重合度ポリマを用いる。又通常、産業用ポリア
ミド繊維に用いられる耐熱剤を含み、例えば無機、有機
の銅塩、ハロゲン化アルカリ金属、ハロゲン化アルカリ
土類金属、無機又は有機のリン化合物、アミン又はフェ
ノール系抗酸化剤等であり、これらの1種又は2種以上
を含む。The fiber used in the present invention consists essentially of a polyamide consisting of polyhexamethylene adipamide, and contains a copolymer or blend polymer containing 95 mol % or more of hexamethylene adipamide units. Examples of polymer components that can be copolymerized include ε-capramide, hexamethylene sebacamide, hexamethylene terephthalamide, hexamethylene isophthalamide, etc., and examples of polymers that can be blended include ε-capramide, hexamethylene sebacamide, hexamethylene terephthalamide, and hexamethylene isophthalamide. There is a polymer that In order to obtain the high strength tire cord of the present invention, the temperature must be 25°C.
A high polymerization degree polymer having a sulfuric acid relative viscosity of 60 or more measured at 1% by weight of the polymer is used. It also usually contains heat-resistant agents used in industrial polyamide fibers, such as inorganic or organic copper salts, alkali metal halides, alkaline earth metal halides, inorganic or organic phosphorus compounds, amine or phenolic antioxidants, etc. and includes one or more of these.
上記ポリマは溶融紡糸されるが、例えばエクストルーダ
ー型紡糸機によってポリマの融点以上例えば280〜3
20℃で紡糸される。The above polymer is melt-spun, using an extruder-type spinning machine, for example, to a temperature higher than the melting point of the polymer, e.g.
Spun at 20°C.
口金(1)を通して紡糸された糸条(y)は冷却チムニ
−(3)によって冷風を吹きつけられて冷却固化された
のち、潤滑剤を付与され、次いで引取ロール(5,6J
で速度を決定されたのち捲取られる。The thread (y) spun through the spinneret (1) is cooled and solidified by being blown with cold air by the cooling chimney (3), and then lubricated with a take-up roll (5.6J
After determining the speed, it is rolled up.
紡糸安定性をよくする為、口金直下tこ徐冷ゾーン(イ
)を5〜50cM、好ましくは10〜40α設ける。通
常は長さ5〜30作の円筒状の加熱筒(2)をとりつけ
る。徐冷ゾーンを通過した糸条は加熱筒の下にとりつけ
た前記冷却チムニ−によって10〜40℃の冷風で急冷
される。In order to improve the spinning stability, a slow cooling zone (a) is provided directly below the spinneret with a thickness of 5 to 50 cM, preferably 10 to 40 cM. Usually, a cylindrical heating cylinder (2) with a length of 5 to 30 pieces is attached. The yarn that has passed through the slow cooling zone is rapidly cooled with cold air at 10 to 40°C by the cooling chimney installed below the heating cylinder.
本発明のポリへキサメチレンアジパミドポリマは溶融紡
糸され、固化されるまでの結晶化温度領域eこ長時間滞
留すると球晶を生成し、紡糸延伸性を悪化させ、強伸度
も低下する。その為前記急冷方法に留意すると共しこ引
取糸の単糸繊度が一定の太さ以上とならないことが必要
である。即ち15〜60デニール(dJとする。6゜6
以上では球晶の生成が著しく、本発明コード用原糸とし
て不適である。1.5 d以下では紡糸時に糸ゆれ、単
糸衝突などが起り正常な紡糸ができない、尚、本発明の
紡糸範囲に於て単糸繊度が一定以上とならないよう(こ
し、球晶生成を防ぐ為3こは口金から吐出される1孔当
りのポリマの吐出量(以後単孔吐出量という)は10〜
30g/分、好ましくは15〜2.5g/dとする。The polyhexamethylene adipamide polymer of the present invention is melt-spun and remains in the crystallization temperature range for a long period of time until it is solidified, producing spherulites, deteriorating the spinning drawability and decreasing the strength and elongation. . Therefore, when paying attention to the above-mentioned quenching method, it is necessary that the single yarn fineness of the drawn yarn does not exceed a certain thickness. That is, 15 to 60 denier (dJ.6゜6
In the above case, the formation of spherulites is significant and the fiber is unsuitable as a yarn for the cord of the present invention. If it is less than 1.5 d, yarn wobbling, single fiber collision, etc. will occur during spinning, and normal spinning will not be possible.In addition, within the spinning range of the present invention, the fineness of single fibers should not exceed a certain level (by straining and preventing spherulite formation). Therefore, the amount of polymer discharged from the nozzle per hole (hereinafter referred to as single hole discharge amount) is 10~
The rate is 30 g/min, preferably 15 to 2.5 g/d.
紡糸速度は引取糸の特性に於て△nが42×10−′以
上、好ましくは45Xi O’以上、ρがt i 58
g/CC以十、以上しくは1140g/Cr−以上、
Eが60%以下、好ましくは50%以下となるよう決定
する。The spinning speed is such that △n is 42 x 10-' or more, preferably 45Xi O' or more, and ρ is t i 58 in terms of the characteristics of the drawn yarn.
g/CC or more, or 1140 g/Cr or more,
E is determined to be 60% or less, preferably 50% or less.
引取糸の特性は前記紡出後の徐冷ゾーンの条件(長さ、
温度)及び急冷の程度及び単糸;1度等紡糸パラメータ
eこよって変化するが、通常は501J Om/分以」
二で上記特性が得られる。より好ましい紡糸速度は65
00 m7分以上である。The characteristics of the drawn yarn depend on the conditions of the slow cooling zone after spinning (length,
(temperature), degree of quenching, and single yarn; 1 degree spinning parameter (e) varies depending on this, but usually 501 J Om/min or more.
2, the above characteristics can be obtained. A more preferable spinning speed is 65
00 m 7 minutes or more.
上記特性を満足しない原糸を用いると、本発明ポリアミ
ドコード特性を満足させる為3こは撚糸以降の工程を1
4害なく通過させることが困難であり、あるいは満足す
るポリアミドコード特性が得られない。紡糸速度の上限
は紡糸引取技術及び装置の開発と共に上昇しつつあるが
現在は8500 m7分まで可能である。If a yarn that does not satisfy the above characteristics is used, in order to satisfy the characteristics of the polyamide cord of the present invention, 3 steps after twisting will be required.
4. It is difficult to pass through the cord without harm, or satisfactory polyamide cord properties cannot be obtained. The upper limit of spinning speed is increasing with the development of spinning take-off technology and equipment, but is currently possible up to 8500 m7 minutes.
上記引取糸(原糸)は一旦捲取機(7)で捲取る原糸は
最終処理コード繊度が目標とする繊度に合致するよう必
要に応じて数本合わせたのち又は合わせたら合撚糸して
生コードとする。下撚と上撚は逆方向とし、撚係数に、
が220D〜2800の範囲で行なう。生コードの撚係
数に1は次式で求めた値である。The above-mentioned drawn yarn (original yarn) is once wound up by the winding machine (7), and after combining several yarns as necessary so that the final treatment cord fineness matches the target fineness, or after combining them, they are combined and twisted. Use raw code. The first twist and the first twist are in opposite directions, and the twist coefficient is
is in the range of 220D to 2800. The twist coefficient of the raw cord is 1, which is a value determined by the following equation.
K+ = T17下T
(ここでT1は10m当り撚数、Dlは生コードの繊度
)
撚係数に1が2800を超えると二重ヨリが発生したり
、又処理コードとした時本発明コードの強力eこ達しな
い。K+ = T17 lower T (here, T1 is the number of twists per 10 m, and Dl is the fineness of the raw cord) If the twist coefficient of 1 exceeds 2800, double twist may occur, or the strength of the cord of the present invention when treated cord is I can't reach this.
一方に、が220θ未満の時は処理コードの耐疲労性が
劣り、不発明の目的を達しない。On the other hand, when is less than 220θ, the fatigue resistance of the treated cord is poor and the object of the invention cannot be achieved.
−12−
次いて」二記生コードは、ぞのまま又は一旦スダレ織t
こしたのち、接着剤を付与する為ディップ液中を通過さ
せたのち、緊張熱処理する。接着剤は通常のレゾルシン
・ホルマリン・ラテックス液を用いる。接着剤の付着量
は2〜5%程度であり、従来コードと同様である。次い
でコードは乾燥ゾーンを通過したのち、緊張熱処理され
るが、これらは通常連続して行なわれる。-12- Next, the 2nd grade student code can be changed as it is or once it is sudare woven.
After straining, it is passed through a dip solution to apply adhesive, and then subjected to tension heat treatment. The adhesive used is ordinary resorcinol, formalin, and latex liquid. The amount of adhesive applied is about 2 to 5%, which is the same as that of conventional cords. The cord then passes through a drying zone and is then subjected to tension heat treatments, which are usually carried out successively.
従来のコードの緊張熱処理はホットゾーンで約1.0%
スl−vツチを与えたのちノルマルゾーンで数%以下の
緊張又は弛緩熱処理される。本発明コードの緊張熱処理
はストレッチ率が50〜100%、好ましくは50〜7
0%であり、従来コードの処理と比較してi%い。従っ
て従来の設備を用いる場合はストレッチの配分を考L6
することが好ましい。例えば乾燥ゾーンでも30%以下
のストレッチを行なうことが好ましい。Conventional cord tension heat treatment is approximately 1.0% in the hot zone.
After applying the stress, the material is subjected to a stress or relaxation heat treatment of a few percent or less in a normal zone. The tension heat treatment of the cord of the present invention has a stretch rate of 50 to 100%, preferably 50 to 7.
0%, which is i% lower than the conventional code processing. Therefore, when using conventional equipment, consider the distribution of stretching L6
It is preferable to do so. For example, it is preferable to perform stretching of 30% or less even in the dry zone.
各ゾーンの前処j」温度は従来のコードを処理する場合
と基本的に変更する必要はないが、本発明コードは従来
のコードのよう(こ延伸時の熱履歴を受げていないか、
一部しか受けていないので、若干品温および又は熱処理
時間を長くすることが好ましい。例えば225〜245
℃、滞留時間を80〜240秒とすることが好ましし\
。The pretreatment temperature in each zone basically does not need to be changed from that when processing conventional cords, but the cords of the present invention do not undergo the same thermal history during stretching as conventional cords.
Since only a portion of the product has been processed, it is preferable to slightly increase the product temperature and/or heat treatment time. For example 225-245
℃, and the residence time is preferably 80 to 240 seconds\
.
本発明コードはハイモジュラス、寸法安定性が改善され
ているが、ハイモジュラスとは収縮率が低い為に緊張率
を高めてハイモジュラスコードとしても寸法安定性が保
持されることを意味する。The cord of the present invention has high modulus and improved dimensional stability, and high modulus means that the shrinkage rate is low, so the tension rate is increased and dimensional stability is maintained even as a high modulus cord.
即ち、タイヤ成型工程で熱収縮処理をうけても、収縮率
が小さい為、当初のコードモジュラスが比較的保持され
ることを意味する。In other words, even if the tire is subjected to heat shrinkage treatment during the tire molding process, the shrinkage rate is small, so the original cord modulus is relatively maintained.
そこで本発明では処理コード1zi) M D Eを8
%以下となるよう緊張熱処理する。好ましいMDEの範
囲は55〜75%である。従来のコードでは」二記MD
Eとなるよう処理をすると収面率が冒くなり、又耐疲労
性も著しく低下する為意味がない。Therefore, in the present invention, the processing code 1zi) M D E is changed to 8
% or less. The preferred MDE range is 55-75%. In the conventional code, "2nd MD"
If the treatment is carried out to obtain E, the yield rate will be affected and the fatigue resistance will also be significantly lowered, so there is no point.
MDKが上記となるよう処理した本発明コードは下記特
性を有する。The code of the present invention processed so that the MDK becomes as described above has the following characteristics.
(イ) T/D≧6.5g/d
(ロ) MDE ≦ 8 %
(ハ) ハS≦4%
(ニ) MDE +△S ≦ 12 %1M)1
9002に≧1000
即ち、本発明コードはMDE 、△S、Kがそれぞれ従
来のタイヤコードに比較して小さいことを特徴とする。(a) T/D≧6.5g/d (b) MDE≦8% (c) HaS≦4% (d) MDE +△S≦12%1M)1
9002≧1000 That is, the cord of the present invention is characterized in that MDE, ΔS, and K are each smaller than those of the conventional tire cord.
そして従来のポリアミドコードの特徴である高強力、高
接着性、高耐疲労性等を保有している。It also possesses the characteristics of conventional polyamide cords, such as high strength, high adhesiveness, and high fatigue resistance.
本発明のポリアミドタイヤコードは上記有用な特性を活
かして、タイヤコード以外の用途、例えばvベルト、タ
イミングベルト、搬送用ベルト等のゴム補強材や樹脂コ
ーティング基布など補強材としても用いることができる
。By taking advantage of the above-mentioned useful properties, the polyamide tire cord of the present invention can be used for purposes other than tire cords, such as rubber reinforcing materials for V-belts, timing belts, conveyor belts, etc., and reinforcing materials for resin-coated base fabrics. .
以下実施例によって本発明を説明する。The present invention will be explained below with reference to Examples.
実施例−1
耐熱剤として酢酸銅0.05重量%及びヨウ化カリウム
10重量%を含む硫酸4目対粘度52のポリへキザメチ
レンアジパミドボリマーをエクストルーダー型紡糸機に
よって溶融紡糸した。Example 1 A polyhexamethylene adipamide polymer having a sulfuric acid 4-viscosity ratio of 52 and containing 0.05% by weight of copper acetate and 10% by weight of potassium iodide as heat-resistant agents was melt-spun using an extruder-type spinning machine.
第1図の装置aを用いポリマ一温度300℃、口金は孔
径05期φ、孔数96ホールを用いた。Using the apparatus a shown in FIG. 1, the polymer temperature was 300° C., and the die had a hole diameter of 05 φ and 96 holes.
口金直下eこ長さ20備の加熱筒をとりつけ、雰囲気温
度(最外周糸条から1備の位置で測温)を500℃とし
た。口金面 度が5〜あったので口金面から加熱筒下端
までの徐冷ゾーンは25mであった。加熱筒の下eこは
1mの断熱板を介して40α長さの環状型チムニ−をと
りつけ、25℃の冷風を風速40m/分で糸条の外周よ
り均一に吹きつけ急冷した。糸条は固化後ガイド給油装
置で潤滑剤を伺与したのち、同速で回転するTGR12
G RiCよって紡速75[10m/分で引取られ、一
旦捲敢機で捲取られた。A heating tube with a length of 20 mm was attached directly below the cap, and the ambient temperature (temperature measured at a position 1 tube from the outermost thread) was set at 500°C. Since the degree of the cap surface was 5~5, the annealing zone from the cap surface to the bottom end of the heating cylinder was 25 m. An annular chimney with a length of 40α was attached to the bottom of the heating cylinder via a 1 m heat insulating plate, and 25° C. cold air was uniformly blown from the outer circumference of the yarn at a wind speed of 40 m/min to rapidly cool the yarn. After the yarn is solidified, it is lubricated with a guide lubricant, and then transferred to the TGR12, which rotates at the same speed.
It was taken over by G RiC at a spinning speed of 75 [10 m/min] and was once wound up by a winding machine.
不テストではポリマ吐出量を変更して単糸繊度の異なる
ものを紡糸した。得られた引取糸は合糸したのち下撚及
び−ヒ撚をそれぞれ撚数を変えて行ンよい、生コードと
した。合糸数は処理コード繊度が従来のコードと同様約
27006となるよう逆算して決定した。次いで生コー
ドはコンビュートリータ(リノラー社製(米))でRF
L液に浸漬したのち、160℃のドライブーンで80秒
間乾燥され、次いで240℃のホットゾーンで80 秒
11jJ、240℃のノルマルゾーンで80秒間熱処理
された。コードはそれぞれの処理ゾーンでストレッチさ
れ、所定のMDEとなるよう緊張熱処理された。In non-tests, the amount of polymer discharged was changed and yarns with different finenesses were spun. After the obtained drawn yarn was double-twisted, the first twist and the second twist were performed by changing the number of twists to obtain a raw cord. The number of yarns to be folded was determined by back calculation so that the fineness of the treated cord would be approximately 27,006, which is the same as that of the conventional cord. Next, the raw code is RF-processed using a Combutreater (manufactured by Rinolar Co., Ltd. (USA)).
After being immersed in the L solution, it was dried in a dry oven at 160°C for 80 seconds, then heat-treated in a hot zone at 240°C for 80 seconds and then in a normal zone at 240°C for 80 seconds. The cord was stretched in each treatment zone and tension heat treated to a predetermined MDE.
比較の為、上記と同じ方法で得られた紡糸速度5 s
o o m/fl糸及び市販のタイヤコード用ポリヘキ
サメチレンアジパミド繊維(+260テニール、204
フイラメント)を2本合撚糸し、接着剤付与及び緊張熱
処理した。For comparison, the spinning speed was 5 s obtained using the same method as above.
o o m/fl yarn and commercially available polyhexamethylene adipamide fiber for tire cord (+260 tenier, 204
Two filaments (filaments) were twisted together, applied with adhesive, and subjected to tension heat treatment.
不発明の特定の物性を有する引取糸を用いて撚係数及び
緊張熱処理を本発明条件で行った場合ノミ、バランスの
よいすぐれた特性を有するポリアミドタイヤコードが得
られた。When the twist coefficient and tension heat treatment were carried out under the conditions of the present invention using drawn yarn having specific physical properties not disclosed in the invention, a polyamide tire cord having excellent, well-balanced properties was obtained.
図面は本発明のコードに供する原糸の製造工程を示す@ 1・・・・・口金 2 ・・・・加熱筒 20 ・・・・・徐冷ゾーン 3 ・・・・冷却チムニ− 4・・・給油装置 5・・・・・引取コテ−ロール 6 ・・・・引取ボデーロール 7・・・・・捲取機 Y・・・・・糸条 The drawing shows the manufacturing process of the yarn used for the cord of the present invention. 1...Base 2...Heating cylinder 20...Slow cooling zone 3... Cooling chimney 4...Lubrication device 5... Pick up roll 6 ・・・Collection body roll 7... Winding machine Y... Thread
Claims (1)
ミドを紡糸速度5o o o m/分以上で溶融紡糸し
て得た伸度Eが60%以下、複屈折△nが42Xi O
’以上、密度ρが1138(g/工)以」二、単糸繊度
Dfが15〜6デニールのマルチフィラメントを延伸す
ることなく、撚係数Kが2200〜2800で上撚及び
下撚を施して生コードとなし、次いで接着剤を付与した
のち、30〜100%のストレッチをかけて緊張熱処理
して下記特性を有する処理コードとすることを特徴とす
るポリアミドタイヤコードの製造方法。 (イ) T/D ≧ 6.5g/d(口I
MDE ≦ 8 %(ハ) △S ≦
4 % し+ MDE +へS≦ 12 第1−k)19
00 ≧ K、E:1000(但し上記(イ)〜0ス
)に於てT/l)は強度、MDKは中間伸度、△Sは1
77℃における乾熱収縮率であり、定義及び測定法は本
文の記載による。)[Claims] Polyamide consisting essentially of polyhexamethylene adipamide is melt-spun at a spinning speed of 5 o o o m/min or more, and has an elongation E of 60% or less and a birefringence △n of 42Xi. O
``The density ρ is 1138 (g/work) or more'' 2. The multifilament with a single yarn fineness Df of 15 to 6 deniers is subjected to ply twisting and first twisting with a twist coefficient K of 2200 to 2800 without drawing. A method for manufacturing a polyamide tire cord, which comprises forming a raw cord, applying an adhesive, stretching the cord by 30 to 100% and subjecting it to tension heat treatment to obtain a treated cord having the following properties. (B) T/D ≧ 6.5g/d (mouth I
MDE ≦ 8% (c) △S ≦
4 % + MDE + S≦ 12 1st-k) 19
00 ≧ K, E: 1000 (T/l in (a) to 0s above) is strength, MDK is intermediate elongation, △S is 1
It is the dry heat shrinkage rate at 77°C, and the definition and measurement method are as described in the text. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6119483A JPS59187640A (en) | 1983-04-07 | 1983-04-07 | Polyamide tire cord and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6119483A JPS59187640A (en) | 1983-04-07 | 1983-04-07 | Polyamide tire cord and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59187640A true JPS59187640A (en) | 1984-10-24 |
Family
ID=13164112
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6119483A Pending JPS59187640A (en) | 1983-04-07 | 1983-04-07 | Polyamide tire cord and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59187640A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5194380A (en) * | 1988-07-12 | 1993-03-16 | Daicel Chemical Industries, Ltd. | Process for the production of optically active 2-hydroxy-4-phenyl-3-butenoic acid |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5434415A (en) * | 1977-08-23 | 1979-03-13 | Toyobo Co Ltd | Production of dipped cord of nylon 6 |
JPS588119A (en) * | 1981-07-03 | 1983-01-18 | Asahi Chem Ind Co Ltd | Polyester fiber suitable for reinforcing rubber |
JPS5854018A (en) * | 1981-09-17 | 1983-03-30 | Toray Ind Inc | Polycapramide fiber and its production |
-
1983
- 1983-04-07 JP JP6119483A patent/JPS59187640A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5434415A (en) * | 1977-08-23 | 1979-03-13 | Toyobo Co Ltd | Production of dipped cord of nylon 6 |
JPS588119A (en) * | 1981-07-03 | 1983-01-18 | Asahi Chem Ind Co Ltd | Polyester fiber suitable for reinforcing rubber |
JPS5854018A (en) * | 1981-09-17 | 1983-03-30 | Toray Ind Inc | Polycapramide fiber and its production |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5194380A (en) * | 1988-07-12 | 1993-03-16 | Daicel Chemical Industries, Ltd. | Process for the production of optically active 2-hydroxy-4-phenyl-3-butenoic acid |
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